This invention relates to hydrophilic, curable, alkoxylated silicone polymers for surface modification and are useful in, e.g., fiber and fabric care, hair care, skin care, pet care, hard surface care, soft surface care, and car care compositions. The compounds are curable silicone polymers which contain one or more polyalkyleneoxy groups, preferably pendant groups, comprising at least some ethyleneoxy units, said polyalkyleneoxy pendant groups are preferably capped with low molecular weight non-reactive capping groups, such as C1-C6 alkyl groups. These compounds are substantive to the surface but keep the surface hydrophilic.
Curable silicones comprise silicones having reactive functional groups that can further condense to form higher molecular weight polymers. One type of curable silicones of particular interest is the so-called room temperature vulcanizable (RTV) silicones that typically undergo condensation involving silanol functions. The silanol functions can be produced from other reactive functional groups, usually through reaction with water. Typical reactive functional groups include Sixe2x80x94H, Sixe2x80x94OH, and Sixe2x80x94OR groups, wherein R is typically a low molecular weight alkyl group or an acyl group. Two reactive functional groups of two separate silicone polymeric molecules, usually in the presence of moisture, can condense to form an Sixe2x80x94Oxe2x80x94Si bond, thus in effect extending the silicone molecular backbone and forming a new silicone with higher molecular weight. The reactive functional groups can also form covalent bonds with the different surfaces to which the silicones are applied, when such surfaces have suitable functional groups that can react with the reactive functional groups of the silicones. Many curable silicones also contain amine functional groups to provide catalysis for the condensation reaction and/or additional surface substantivity benefit. These properties make curable silicones useful in surface protection and/or modification.
Curable amine functional silicones are broadly used in, e.g., car waxes and polishes to protect, e.g., painted, rubber and vinyl surfaces, such as those disclosed in U.S. Pat. No. 3,960,575 issued Jun. 1, 1976 to Martin, U.S. Pat. No. 3,576,779 issued Apr. 27. 1971 to Holdstock et al., said patents are incorporated herein by reference. Noncurable aminofunctional silicones are also disclosed for use in car care, such as U.S. Pat. No. 4,247,330 issued Jan. 27, 1981 to Sanders, said patent is incorporated herein by reference. Other applications are known. U.S. Pat. Nos. 4,800,026 issued Jan. 24, 1989 and 4,911,852 issued Mar. 27, 1990 to Coffindaffer et al. discloses the use of curable amino functional silicones for fabric wrinkle reduction; U.S. Pat. No. 4,419,391 issued Dec. 6, 1983 to Tanaka et al., discloses the use of curable amino silicones to impart fabrics with softness, slipperiness and sliminess; U.S. Pat. No. 5,098,979 issued Mar. 24, 1992 and U.S. Pat. No. 5,196,499 Issued Mar. 23, 1993 to O""Lenick, disclose noncurable polyethoxylated silicones with polyethoxylate groups capped by cationic groups comprising long chain alkyl groups for use as softener actives; said patents describe various examples of curable amino functional silicones, and are incorporated herein by reference. U.S. Pat. No. 5,091,105 issued Feb. 25, 1992 to Madore et al. discloses the use of hydrophobic curable silicones not containing amino substituents to provide fabric softening benefit in liquid detergent compositions; said patent is incorporated herein by reference.
Typical curable silicones, such as curable amine functional silicones, are surface substantive and make the treated surface very hydrophobic. The surface hydrophobicity is a desired property for some applications, such as car care. A car painted surface treated with curable silicone-containing wax is very water repellent, and causes water to bead up to form distinctive water drops on the car painted surface. This phenomenon is used as a signal for the protection benefit of the wax treatment.
However, the surface hydrophobicity, water repellent property is not desirable in other applications. When a car is treated with curable silicones and then exposed to rain or splashed water on the road, the water drops on the car surface frequently contain dirt and other soils that become visible when these distinctive water drops dry out. This results in nonuniformly soiled spots on the surface that are unsightly and undesirable. On the other hand, a hydrophilic car surface provides a sheeting action with which rain or splashed water can wet and spread across the car surface uniformly, forming a continuous film that is largely drained away and helps the soil run off, or at least spreads the soil more uniformly on the car surface. When the car surface dries out, the soil, if any, is distributed more uniformly, and becomes significantly less visible and more acceptable.
For normal usage, waterproofing of garments and other household fabrics such as towels is also not desirable and should be avoided.
Therefore, it is desirable for many applications, such as in and fabric care, hair care, skin care, pet care, and car care compositions, to have silicone polymers as surface modifiers that keep or make the treated surface hydrophilic. Thus the present invention relates to curable silicones that are surface substantive, but without the accompanying hydrophobicity negative. This surface substantivity results in long lasting benefits, such as fabric color restoration, fabric softening, fabric conditioning, wrinkle control, soil release, and antistatic properties, without the fabrics becoming hydrophobic. It also results in, e.g., long lasting car care benefits, e.g., shine/gloss, color deepening, glide/lubricity, and long lasting hair care benefits, such as shine and easy combing.
The present invention relates to a class of novel curable silicone polymers comprising:
(a) one or more reactive Si functional groups including Sixe2x80x94H, Sixe2x80x94OH, Sixe2x80x94OR and/or Sixe2x80x94OCOR groups, wherein R is typically a low molecular weight alkyl group;
(b) one or more polyalkyleneoxy groups comprising at least some ethyleneoxy units, said polyalkyleneoxy groups can be part of the polymer backbone, terminal groups (situated at the ends of the silicone polymer backbone), pendant groups, and mixtures thereof, with polyalkyleneoxy terminal and/or pendant groups being preferably capped with low molecular weight nonreactive capping groups, such as C1-C6 alkyl groups, but optionally can be reactive terminal groups, preferably in hindered or protected form that avoid excessive crosslinking prior to application; and
(c) optionally but preferably one or more cationic nitrogen functional groups, being pendant groups, terminal groups, and/or part of the polymer backbone, and mixtures thereof, said cationic nitrogen functional group comprises, e.g., amine functional groups, imine functional groups, imidazole functional groups, imidazoline functional groups; quaternary ammonium functional groups, polycationic groups, and the like, and mixtures thereof.
Each reactive Si bearing a reactive functional group can be either a terminal group or within the silicone backbone. It can also optionally be on a pendant group. Each polyalkyleneoxy group can also be in various positions in the silicone polymer, including: (a) as pendant group linked to the silicone backbone by a linking group, preferably being a hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2xe2x80x94, -phenylene-CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, or an aminoalkylene group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group and xe2x80x94CH2CH(CH3)CH2xe2x80x94N less than  group, providing that no Oxe2x80x94O or Nxe2x80x94O bonds are formed; (b) as terminal group on the silicone, especially linked to the terminal Si atom by the same linking groups listed in (a) hereinabove; (c) as an internal group, incorporated into the main silicone chain by links selected from the linking groups listed in (a) hereinabove, providing that no Oxe2x80x94O bonds are formed; and (d) mixtures thereof. Each optional cationic nitrogen functional group can also be in various positions in the silicone polymer, including: (a) as pendant group linked to the silicone backbone by a linking group, preferably being a hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, -phenylene-CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, or an aminoalkylene group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group and xe2x80x94CH2CH(CH3)CH2xe2x80x94N less than  group, providing that no Nxe2x80x94N or Nxe2x80x94O bonds are formed; (b) as terminal group on the silicone, especially linked to the terminal Si atom by the same groups listed in (a) above; (c) as an internal group, incorporated into the main silicone chain by links selected from the linking groups listed in (a) hereinabove and/or polyalkyleneoxy groups, providing that no Nxe2x80x94N or Nxe2x80x94O bonds are formed; (d) as terminal group on the end of a polyalkeneoxy terminal or pendant group, and linked to the polyalkeneoxy group through a hydrocarbon or oxygenated hydrocarbon linking group such as a xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94 or xe2x80x94CH2CH(OH)CH2xe2x80x94 group; and (e) mixtures thereof. The silicone polymer of the present invention can also preferably comprise at least two types of polyalkyleneoxy groups, selected from the group consisting of terminal group, pendant group, and/or internal polyalkyleneoxy group, and mixtures thereof. Similarly, the silicone polymer of the present invention can preferably comprise at least two types of optional cationic nitrogen groups, selected from the group consisting of pendant group, internal group, terminal group, and/or terminal group on the end of a polyalkeneoxy terminal or pendant group, and mixtures thereof.
The silicone polymers of the current invention conform to the following general structure:
(R1)aR3xe2x88x92aSixe2x80x94(xe2x80x94Oxe2x80x94SiR2)mxe2x80x94(xe2x80x94Oxe2x80x94SiRA)nxe2x80x94(xe2x80x94Oxe2x80x94SiRB)pxe2x80x94(xe2x80x94Oxe2x80x94SiRD)qxe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]rxe2x80x94Oxe2x80x94Si(R1)bR3xe2x88x92b
wherein:
each R group is the same or different and is preferably an alkyl, aryl, and mixtures thereof, more preferably, each R is methyl, ethyl, propyl, butyl, or phenyl group, most preferably R is methyl;
each A of the Si reactive functional group is the same or different and is preferably selected from the group consisting of hydrogen, xe2x80x94OH, xe2x80x94OR, xe2x80x94OCOCH3, xe2x80x94CH2CH2Si(OR)3, xe2x80x94CH2CH2Si(OR)2R, xe2x80x94CH2CH2Si(OR)R2, and mixtures thereof;
each optional, but preferred cationic B group is an xe2x80x94Xxe2x80x94E group with each X being a hydrocarbon or oxygenated hydrocarbon linking group, preferably being selected from the group consisting of xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, and mixtures thereof; and each E being a cationic nitrogen functional group, preferably being selected from the group consisting of amino group and quaternary ammonium derivatives thereof; cyclic amino group and quaternary ammonium derivatives thereof; imidazole group and imidazolium derivatives thereof; imidazoline group and imidazolinium derivatives thereof; polycationic group, and mixtures thereof;
each optional D group is a poly(ethyleneoxy/propyleneoxy) group having the general structure:
xe2x80x94Zxe2x80x94O(C2H4O)c(C3H6O)dR3
wherein each Z is a linking group, preferably selected from the group consisting of hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, -phenylene-CH2CH2xe2x80x94 and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94; aminohydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group; xe2x80x94CH2CH(CH3)CH2xe2x80x94N less than  group, and mixtures thereof; each R3 group is the same or different and being preferably selected from the group consisting of hydrogen, R, JE, xe2x80x94CH2CH(R)OH, xe2x80x94CH2C(R)2OH, xe2x80x94CH2CH(OH)CH2OR, xe2x80x94CH2CH(OH)CH2(OCH2CH2)eOR, tetrahydropyranyl, xe2x80x94CH(R)OR, C(O)H, and/or xe2x80x94C(O)R group, more preferably R3 group is an R group, with R being more preferably selected from methyl and/or ethyl group; each c is at least 2, preferably at least about 5, more preferably at least about 11, even more preferably at least about 21, total c (that is the sum of all of the ethyleneoxy units in the polymer, including all polyalkyleneoxy side groups) has a value of from about 4 to about 2500, preferably from about 6 to about 1000, more preferably from about 11 to about 800, and even more preferably from about 21 to about 500; total d is from 0 to about 1000, preferably from 0 to about 300; more preferably from 0 to about 100, and even more preferably d is 0; total c is preferably equal or larger than total d; total c+d has a value of from about 4 to about 2500, preferably from about 8 to about 800, and more preferably from about 15 to about 500; and each e is from 1 to about 20, preferably 1 or 2;
each optional G is xe2x80x94O(C2H4O)v(C3H6O)wxe2x80x94; each J is selected from X and xe2x80x94CH2CH(OH)CH2xe2x80x94; each optional E is a cationic group defined as hereinabove; each v is from 0 to about 200, preferably from about 5 to about 150, more preferably from about 11 to about 120, and even more preferably from about 20 to about 100; each w is from 0 to about 50 and preferably v is equal or larger than w; each g and k is from 0 to about 10, preferably from 0 to about 6, more preferably from about 1 to about 3, and even more preferably from about 1 to about 2; j is g+kxe2x88x921, providing that no Oxe2x80x94O bonds are formed;
each R1 group is the same or different and is preferably selected from the group consisting of R, A, B, and/or D group;
each a and/or b is an integer from 0 to 3, preferably 2, more preferably 1;
m is from about 5 to about 1600, preferably from about 6 to about 800, more preferably from about 8 to about 400, and even more preferably from about 10 to about 200;
n, a, and b, and the R1 groups of the terminal groups (R1)aR3xe2x88x92aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3xe2x88x92b are selected such that the silicone polymer comprises at least one reactive Si functional group in the form of an Sixe2x80x94A group, preferably Sixe2x80x94H, Sixe2x80x94OH, Sixe2x80x94OR, Sixe2x80x94OCOR, and mixtures thereof, with R preferably a methyl group; and more preferably the silicone molecule comprises at least about two reactive Si functional groups; with typically the n to (m+n) ratio (and the n to (m+n+p) ratio when p is not 0), ranges from 0 to about 1:2, preferably from about 1:1500 to about 1:3, more preferably from about 1:400 to about 1:4, and even more preferably from about 1:100 to about 1:4;
p, a, and b, and the R1 groups of the terminal groups (R1)aR3-aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3xe2x88x92b are selected such that the silicone polymer optionally comprises at least one cationic group in the form of an Sixe2x80x94B group; with typically the p to (m+n+p) ratio ranges from 0 to about 1:2, preferably from about 1:200 to about 1:3, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:4; and
q, a, and b, and the R1 groups of the terminal groups (R1)aR3xe2x88x92aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3xe2x88x92b are selected such that the silicone polymer comprises at least one cationic poly(ethyleneoxy/propyleneoxy) Sixe2x80x94D group; and preferably at least about two Sixe2x80x94D groups; with typically the q to (m+n+p) ratio ranges from about 1:1000 to about 1:3, preferably from about 1:200 to about 1:4, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:5;
r is from 0 to about 100, and is preferably 0; when r is greater than 0, it is preferably from 1 to about 20, more preferably from 1 to about 10, with r being 0 when neither a polyalkyleneoxy group nor a cationic group is part of the polymer backbone; when one or more polyalkyleneoxy groups and/or cationic groups are part of the polymer backbone, the r to (m+n+p) ratio ranges typically from about 1:1000 to about 1:2, preferably from about 1:500 to about 1:4, more preferably from 1:200 to about 1:8, and even more preferably from about 1:100 to about 1:20;
wherein said silicone polymer can be linear, branched, and/or cyclic, preferably linear or branched, and more preferably linear; and wherein different xe2x80x94Oxe2x80x94SiR2xe2x80x94, xe2x80x94Oxe2x80x94SiRAxe2x80x94, xe2x80x94Oxe2x80x94SiRBxe2x80x94, xe2x80x94Oxe2x80x94SiRDxe2x80x94, and xe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]xe2x80x94 groups can be distributed randomly in the silicone backbone and/or organized as block copolymers of different degrees.
The preferred hydrophilic curable silicones of the present invention comprise poly(alkyleneoxy) D groups, and preferably poly(ethyleneoxy) D groups that are exposed on the treated surface, and not being concealed and hidden within and/or underneath the silicone coating layer. This is achieved by (a) having the poly(ethyleneoxy) groups capped with a C1-C4 alkyl group, a hindered alcohol group, or a protected alcohol group, to prevent the poly(ethyleneoxy) groups from reacting with the reactive Sixe2x80x94A groups to become part of the backbone and/or cross-linking groups, and (b) not having the poly(ethyleneoxy) groups capped with cationic E groups if the poly(ethyleneoxy) groups are short, since cationic E groups are believed to have the tendency to anchor deep on the treated surface and thus also driving the poly(ethyleneoxy) groups deep underneath the silicone coating layer.
The present invention relates to a class of novel curable silicone polymers comprising:
(a) one or more reactive Si functional groups including Sixe2x80x94H, Sixe2x80x94OH, Sixe2x80x94OR and/or Sixe2x80x94OCOR groups, wherein R is typically a low molecular weight alkyl group;
(b) one or more polyalkyleneoxy groups comprising at least some ethyleneoxy units, said polyalkyleneoxy groups can be part of the polymer backbone, terminal groups (situated at the ends of the silicone polymer backbone), pendant groups, and mixtures thereof, with polyalkyleneoxy terminal and/or pendant groups being preferably capped with low molecular weight nonreactive capping groups, such as C1-C6 alkyl groups, but optionally can be reactive terminal groups, preferably in hindered or protected form that avoid excessive crosslinking prior to application; and
(c) optionally but preferably one or more cationic nitrogen functional groups, being pendant groups, terminal groups, and/or part of the polymer backbone, and mixtures thereof, said cationic nitrogen functional group comprises, e.g., amine functional groups, imine functional groups, imidazole functional groups, imidazoline functional groups; polycationic groups, quaternary ammonium functional groups, and the like, and mixtures thereof.
Each reactive Si bearing a reactive functional group can be either a terminal group or within the silicone backbone. It can also optionally be on a pendant group. Each polyalkyleneoxy group can also be in various positions in the silicone polymer, including: (a) as pendant group linked to the silicone backbone by a linking group, preferably being a hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, -phenylene-CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, or an aminoalkylene group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group, providing that no Oxe2x80x94O bonds are formed; (b) as terminal group on the silicone, especially linked to the terminal Si atom by the same linking groups listed in (a) hereinabove; (c) as internal group, incorporated into the main silicone chain by links selected from the linking groups listed in (a) hereinabove, providing that no Oxe2x80x94O bonds are formed; and (d) mixtures thereof. Each optional cationic nitrogen functional group can also be in various positions in the silicone polymer, including: (a) as pendant group linked to the silicone backbone by a linking group, preferably being a hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, -phenylene-CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, or an aminoalkylene group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group, providing that no Nxe2x80x94N or Nxe2x80x94O bonds are formed; (b) as terminal group on the silicone, especially linked to the terminal Si atom by the same groups listed in (a) above; (c) as internal group, incorporated into the main silicone chain by links selected from the linking groups listed in (a) hereinabove and/or polyalkyleneoxy groups, providing that no Nxe2x80x94N or Nxe2x80x94O bonds are formed; (d) as terminal group on the end of a polyalkeneoxy terminal or pendant group, especially linked to the polyalkeneoxy group through a hydrocarbon or oxygenated hydrocarbon linking group such as a xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94 or xe2x80x94CH2CH(OH)CH2xe2x80x94 group; and (e) mixtures thereof. The silicone polymer of the present invention can also preferably comprise at least two types of polyalkyleneoxy groups, selected from the group consisting of terminal group, pendant group, and/or internal polyalkyleneoxy group, and mixtures thereof. Similarly, the silicone polymer of the present invention can preferably comprise at least two types of optional cationic nitrogen groups, selected from the group consisting of pendant group, internal group, terminal group, terminal group on the end of a polyalkeneoxy terminal or pendant group, and mixtures thereof.
The silicone polymers of the current invention conform to the following general structure:
(R1)aR3xe2x88x92aSixe2x80x94(xe2x80x94Oxe2x80x94SiR2)mxe2x80x94(xe2x80x94Oxe2x80x94SiRA)nxe2x80x94(xe2x80x94Oxe2x80x94SiRB)pxe2x80x94(xe2x80x94Oxe2x80x94SiRD)qxe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]rxe2x80x94Oxe2x80x94Si(R1)bR3xe2x88x92b
wherein:
each R group is the same or different and is preferably an alkyl, aryl, and mixtures thereof, more preferably, each R is methyl, ethyl, propyl, butyl, or phenyl group, most preferably R is methyl;
each A of the Si reactive functional group is the same or different and is preferably selected from the group consisting of hydrogen, xe2x80x94OH, xe2x80x94OR, xe2x80x94OCOCH3, xe2x80x94CH2CH2Si(OR)3, xe2x80x94CH2CH2Si(OR)2R, xe2x80x94CH2CH2Si(OR)R2, and mixtures thereof;
each optional, but preferred cationic B group is an xe2x80x94Xxe2x80x94E group with each X being a hydrocarbon or oxygenated hydrocarbon linking group, preferably being selected from the group consisting of xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, and mixtures thereof; and each E being a cationic nitrogen functional group, preferably being selected from the group consisting of amino group and quaternary ammonium derivatives thereof; cyclic amino group and quaternary ammonium derivatives thereof; imidazole group and imidazolium derivatives thereof; imidazoline group and imidazolinium derivatives thereof; polycationic group; and mixtures thereof;
each optional D group is a poly(ethyleneoxy/propyleneoxy) group having the general structure:
xe2x80x94Zxe2x80x94O(C2H4O)c(C3H6O)dR3
wherein each Z is a linking group, preferably selected from the group consisting of hydrocarbon or oxygenated hydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(OH)CH2OCH2CH2CH2xe2x80x94, -phenylene-CH2CH2xe2x80x94 and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94; aminohydrocarbon linking group, e.g., xe2x80x94CH2CH2CH2xe2x80x94N less than  group and xe2x80x94CH2CH(CH3)CH2xe2x80x94N less than  group; and mixtures thereof; each R3 group is the same or different and being preferably selected from the group consisting of hydrogen, R, cationic nitrogen functional E group, xe2x80x94CH2CH(R)OH, xe2x80x94CH2C(R)2OH, xe2x80x94CH2CH(OH)CH2OR, xe2x80x94CH2CH(OH)CH2(OCH2CH2)eOR, tetrahydropyranyl, xe2x80x94CH(R)OR, C(O)H, and/or xe2x80x94C(O)R group, more preferably R3 group is an R group, with R being more preferably selected from methyl and/or ethyl group; each c is at least about 2, preferably at least about 5, more preferably at least about 11, and even more preferably at least about 21, total c (for all polyalkyleneoxy side groups) has a value of from about 4 to about 2500, preferably from about 6 to about 1000, more preferably from about 11 to about 800, and even more preferably from about 21 to about 500; total d is from 0 to about 1000, preferably from 0 to about 300; more preferably from 0 to about 100, and even more preferably d is 0; preferably total c is equal or larger than total d; total c+d has a value of from about 4 to about 2500, preferably from about 8 to about 800, and more preferably from about 15 to about 500; and each e is from 1 to about 20, preferably 1 or 2;
each optional G is xe2x80x94O(C2H4O)v(C3H6O)wxe2x80x94; each J is selected from X and xe2x80x94CH2CH(OH)CH2xe2x80x94; each optional E is a cationic group defined as hereinabove; each v is from 0 to about 200, preferably from about 5 to about 150, more preferably from about 11 to about 120, and even more preferably from about 21 to about 100; each w is from 0 to about 50 and preferably v is equal or larger than w; each g and k is from 0 to about 10, preferably from 0 to about 6, more preferably from about 1 to about 3, and even more preferably from about 1 to about 2; j is g+kxe2x88x921, within the segment designated as (G)gxe2x80x94(J)jxe2x80x94(E)k, the units can be arranged in any order, providing that no Oxe2x80x94O bonds and/or Nxe2x80x94N are formed;
each R1 group is the same or different and is preferably selected from the group consisting of R, A, B, and/or D group;
each a and/or b is an integer from 0 to 3, preferably 2, more preferably 1;
m is from about 5 to about 1600, preferably from about 6 to about 800, more preferably from about 8 to about 400, and even more preferably from about 10 to about 200;
n, a, and b, and the R1 groups of the terminal groups (R1)aR3xe2x88x92aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3xe2x88x92b are selected such that the silicone molecule comprises at least one reactive Si functional group in the form of an Sixe2x80x94A group, preferably Sixe2x80x94H, Sixe2x80x94OH, Sixe2x80x94OR, Sixe2x80x94OCOR, and mixtures thereof, with R preferably a methyl group; and more preferably the silicone polymer comprises at least about two reactive Si functional groups; with typically the n to (m+n) ratio (and the n to (m+n+p) ratio when p is not 0), ranges from 0 to about 1:2, preferably from about 1:1500 to about 1:3, more preferably from about 1:400 to about 1:4, and even more preferably from about 1:100 to about 1:4;
p, a, and b, and the R1 groups of the terminal groups (R1)aR3xe2x88x92aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3xe2x88x92b are selected such that the silicone polymer optionally comprises at least one cationic group in the form of an Sixe2x80x94B group; with typically the p to (m+n+p) ratio ranges from 0 to about 1:2, preferably from about 1:200 to about 1:3, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:4; and
q, a, and b, and the R1 groups of the terminal groups (R1)aR3xe2x88x92aSixe2x80x94Oxe2x80x94 and Oxe2x80x94Si(R1)bR3xe2x88x92b are selected such that the silicone polymer comprises at least one poly(ethyleneoxy/propyleneoxy) Sixe2x80x94D group; and preferably at least about two Sixe2x80x94D groups; with typically the q to (m+n+p+q) ratio ranges from about 1:1000 to about 1:3, preferably from about 1:200 to about 1:4, more preferably from about 1:100 to about 1:4, and even more preferably from about 1:50 to about 1:5;
r is from 0 to about 100, and is preferably 0; when r is greater than 0, it is preferably from 1 to about 20, more preferably from 1 to about 10, with r being 0 when neither a polyalkyleneoxy group nor a cationic group is part of the polymer backbone; when one or more polyalkyleneoxy groups and/or cationic groups are part of the polymer backbone, the r to (m+n+p) ratio ranges typically from about 1:1000 to about 1:2, preferably from about 1:500 to about 1:4, more preferably from 1:200 to about 1:8, and even more preferably from about 1:100 to about 1:20;
wherein said silicone polymer can be linear, branched, and/or cyclic, preferably linear or branched, and more preferably linear; and wherein different xe2x80x94Oxe2x80x94SiR2xe2x80x94, xe2x80x94Oxe2x80x94SiRAxe2x80x94, xe2x80x94Oxe2x80x94SiRBxe2x80x94, xe2x80x94Oxe2x80x94SiRDxe2x80x94, and xe2x80x94[OSiR2xe2x80x94Jxe2x80x94(G)gxe2x80x94(J)jxe2x80x94(E)kxe2x80x94Jxe2x80x94SiR2]xe2x80x94 groups can be distributed randomly in the silicone backbone and/or organized as block copolymers of different degrees.
The preferred hydrophilic curable silicones of the present invention comprise poly(alkyleneoxy) D groups, and preferably said poly(ethyleneoxy) D groups are exposed on the treated surface, and not being concealed and hidden within and/or underneath the silicone coating layer, in order to provide the surface hydrophilicity. This is achieved by (a) having the poly(ethyleneoxy) groups capped with a C1-C4 alkyl group, a hindered alcohol group, or a protected alcohol group, to prevent the poly(ethyleneoxy) groups from reacting with the reactive Sixe2x80x94A groups to become part of the backbone and/or cross-linking groups, and (b) not having the poly(ethyleneoxy) groups capped with cationic E groups if the poly(ethyleneoxy) groups are short, since cationic E groups are believed to have the tendency to anchor deep on the treated surface and thus also driving the poly(ethyleneoxy) groups deep underneath the silicone coating layer. To improve hydrophilicity property, each capping cationic group E, if present, is preferably small, comprising less than about 10 carbon atoms, preferably less than about 8 carbon atoms, more preferably less than about 7 carbon atoms, and even more preferably less than about 6 carbon atoms. To effectively avoid crosslinking or reduce the crosslinking by the poly(alkyleneoxy) D groups, any capping alcohol group needs to have the OH group well protected; therefore tertiary alcohol groups such as xe2x80x94CH2C(R2)OH or hindered secondary alcohol groups, such as xe2x80x94CH2CH(R4)(OH), with R4 not being H or CH3, are preferred. If the capping alcohol groups are not hindered, but readily available, then they can condense with the reactive silicone groups to cause excessive crosslinking resulting in a silicone that can not be solubilized and/or dispersed in the compositions of the present invention.
However, it will be appreciated that large poly(ethylene oxide) groups are less needful of these capping group restrictions, since they are less likely to be completely covered by the silicone segments in the cured layer. Thus, the present invention also relates to hydrophilic curable silicones with uncapped pendant poly(alkyleneoxy) D groups (i.e., poly(alkyleneoxy) D groups terminated by a xe2x80x94OH) and/or capped with cationic E groups to increase crosslinking and/or surface substantivity, wherein each pendant poly(alkyleneoxy) D group preferably comprises at least about 11 ethyleneoxy units (i.e., c being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (c being equal or greater than about 15), more preferably at least about 21 ethyleneoxy units (c being equal or greater than about 21), and more preferably at least about 30 ethyleneoxy units (c being equal or greater than about 30). Similarly, when internal poly(ethyleneoxy) G groups which form part of the polymer backbone are desirable, each G group should preferably comprise at least about 11 ethyleneoxy units (i.e., v being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (v being equal or greater than about 15), more preferably at least about 21 ethyleneoxy units (c being equal or greater than about 21), and more preferably at least about 30 ethyleneoxy units (v being equal or greater than about 30).
Silicones of the type
[AbR(CnH2nO)xCH2xe2x80x94CH(OCnH2n)xRAcxe2x80x94CH2(OCnH2n) xRAd]a
as disclosed in U.S. Pat. No. 4,246,423 issued Jan. 20, 1981 to E. R. Martin, are not part of the present invention because they are claimed to impart hydrophobic property to fabrics; said patent is incorporated herein by reference.
The present invention also relates to the use of the hydrophilic curable silicone polymers of the present invention to treat fabric to provide at least one of the following long lasting fabric care benefits: wrinkle control, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric softness, fabric soiling reduction, fabric soil release, fabric shape retention, ease of ironing, fabric comfort, fabric hydrophilicity, static control, and/or fabric shrinkage reduction.
The hydrophilic curable silicone polymers of the present invention can be formulated as aqueous compositions, such as solutions, emulsions, and/or dispersions. However, since these silicone polymers have reactive functional groups that can condense to form Sixe2x80x94Oxe2x80x94Si bonds in the presence of moisture, it is also preferred to formulate said silicone polymers in anhydrous compositions for long term stability. Examples of preferred compositions are gels, waxes, powders, and anhydrous liquid compositions comprising anhydrous solvents that do not promote crosslinking, such as monohydric alcohols. When a dilute aqueous composition is desirable, it is best to first prepare a concentrated composition containing the desired curable silicone in a suitable anhydrous solvent which is miscible with water, such as anhydrous low molecular weight alcohols, e.g., ethanol, methanol, isopropanol, and mixtures thereof, such a concentrated composition is then diluted with water immediately prior to to the target surface, and then let dry and cure on the surface. Because of this complex procedure, it is preferred to provide the hydrophilic curable silicone polymers of the present invention to the consumer in the form of an article of manufacture comprising an anhydrous composition in association with instructions for use to direct the consumer to properly apply an effective amount of hydrophilic curable silicone polymer to the surface to provide the desired benefits.
For fabric care, the composition of the present invention can be applied to fabric and/or an entire garment via a, e.g., dipping, soaking, misting and/or spraying process, followed by a drying step. The application can be done industrially by large scale processes on textiles and/or finished garments and clothing, or in a consumer""s home by the use of a commercial product. For a fabric care consumer spray product, it is desirable that the spraying and/or misting of the entire garment occurs in a manner such that excessive amounts of the fabric/garment care composition are prevented from being released to the open environment. For example, the spraying and/or misting of the entire garment is done in an enclosed and/or containable space, such as within a bag, a cabinet, or other articles suitable for containing the garment.
The curable silicones of the present invention can also be formulated with or used in conjunction with other reactive silicones or silanes as co-reactants in the curing process. For example, silicones of the present invention can be used with 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, tetraethoxysilane, diacetoxymethyl terminated polydimethylsiloxanes, and the like and mixtures thereof.
The present invention also relates to hydrophilic nonreactive, noncurable cationic silicone polymers comprising cationic amino functional groups and hydrophilic polyalkyleneoxy groups. They have a similar structure as the general structure given hereinabove, with n being 0, and with R1 groups not comprising A groups. These noncurable cationic slicone polymers can provide an intermediate durability benefit which is preferred in some applications. Said noncurable cationic slicone polymers preferably comprise poly(ethyleneoxy) D pendant and/or terminal groups that are exposed on the treated surface, and not being concealed and hidden within and/or underneath the silicone coating layer. This is achieved by (a) having the poly(ethyleneoxy) pendant groups not capped with cationic functional capping groups, (b) when cationic functional groups are needed on the poly(ethyleneoxy) pendant groups, e.g., for improved surface substantivity, each pendant poly(alkyleneoxy) D group should comprise at least about 11 ethyleneoxy units (i.e., c being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (c being equal or greater than about 15), more preferably at least about 21 ethyleneoxy units (c being equal or greater than about 21), and even more preferably at least about 30 ethyleneoxy units (c being equal or greater than about 30), and/or (c) when internal poly(ethyleneoxy) G groups which form part of the polymer backbone are present, each G group should preferably comprise at least about 11 ethyleneoxy units (i.e., v being equal or greater than about 11), more preferably at least about 15 ethyleneoxy units (v being equal or greater than about 15), more preferably at least about 15 ethyleneoxy units (c being equal or greater than about 15), and even more preferably at least about 30 ethyleneoxy units (v being equal or greater than 30).
In this case where there are no reactive Si functions A, and where there are quaternary nitrogen moieties E, in the backbone or on the ends of the backbone (with k greater than 0 and/or R3 being JE) and where there are no pendant cationic groups (p=0), then J shall not comprise groups consisting of ring-opened epoxides. That is, in this special case, J will be selected only from hydrocarbon links, preferably the group consisting of xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94, and xe2x80x94CH2-phenylene-CH2CH2xe2x80x94, and mixtures thereof.
The silicones of the present inventions can preferably comprise polyalkyleneoxy groups as terminal groups, pendant groups, backbone groups (forming part of the polymer backbone), and mixtures thereof.
The present invention also relates to the use of the silicone polymers of the present invention to treat fabric, to provide at least one of the following fabric care benefits: wrinkle control, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric softness, fabric soiling reduction, fabric soil release (both oily and particulate soils), fabric shape retention, ease of ironing, fabric comfort, static control, fabric hydrophilicity, and/or fabric shrinkage reduction. The silicone polymers of the present invention can provide at least some fabric care benefits to all types of fabrics, including fabrics made of natural fibers, synthetic fibers, and mixtures thereof. Nonlimiting examples of fabric types that can be treated with the fabric care compositions of the present invention, to obtain fabric care benefits include fabrics made of (1) cellulosic fibers such as cotton, rayon, linen, Tencel, (2) proteinaceous fibers such as silk, wool and related mammalian fibers, (3) synthetic fibers such as polyester, acrylic, nylon, and the like, (4) long vegetable fibers from jute, flax, ramie, coir, kapok, sisal, henequen, abaca, hemp and sunn, and (5) mixtures thereof.
The present invention also relates to a method for providing a fabric with a fabric care benefit selected from the group consisting of: wrinkle control, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric softness, fabric soiling reduction, fabric soil release, fabric shape retention, ease of ironing, fabric comfort, fabric hydrophilicity, static control, and/or fabric shrinkage reduction, wherein said method comprises contacting said fabric with an effective amount silicone polymers of the present invention to provide a noticeable benefit. In a preferred method, said silicone polymers are provided by using anhydrous compositions or freshly prepared aqueous compositions as described hereinabove. The present invention further relates to the use of the silicone polymers of the present invention to treat fabric, to provide at least one of the following fabric care benefits: wrinkle control, wrinkle resistance, fabric wear reduction, fabric wear resistance, fabric pilling reduction, fabric color maintenance, fabric color fading reduction, fabric color restoration, fabric softness, fabric soiling reduction, fabric soil release, fabric shape retention, ease of ironing, fabric comfort, fabric hydrophilicity, static control, and/or fabric shrinkage reduction. The silicone polymers, compositions, methods, and articles of manufacture comprising said polymers, can provide the benefits hereinabove to both consumer, household fabrics such as clothings, bed linens, curtains, drapes, and the like, and industrial, institutional, and/or commercial fabrics such as uniforms, bed linens, tablecloths, and the like.
Following are nonlimiting examples of hydrophilic curable silicones of the present invention. These materials are prepared from intermediate materials that can be prepared as follows:
Alkoxylated Allyl Alcohols
Ethoxylated(5) Allyl Alcohol, Intermediate Material A To a 250 ml, three neck, round bottom flask equipped with a magnetic stirring bar, condenser, thermometer, and temperature controller (Therm-O-Watch(copyright), I2R) is added allyl alcohol (Aldrich, about 24.5 g, about 0.422 mol, from Aldrich, Milwaukee, Wis.) under argon. Sodium metal (Aldrich, about 0.78 g, about 0.034 mol) is added in three increments. An exotherm occurs (about 60xc2x0 C.), and after the sodium is dissolved, the solution is heated to about 80xc2x0 C. Ethylene oxide gas is added via a sparging tube with rapid stirring. The temperature of the system is kept below about 130xc2x0 C. during the addition of ethylene oxide, which is stopped when a weight gain of about 77.3 g, corresponding to about 4.2 ethoxy units, is obtained. A 1H-NMR(CDCl3) shows resonances for the allyl peaks at xcx9c5.9 ppm (CH2xe2x95x90CHxe2x80x94), xcx9c5.2 ppm (CH2xe2x95x90CHxe2x80x94), and xcx9c4 ppm (CH2xe2x95x90CHCH2xe2x80x94), and a large resonance for the hydrogens from the ethoxy groups at xcx9c3.5-3.8 ppm. Integration of these peaks indicates that the degree of ethoxylation is about 5. The material is neutralized to about pH 7 with methanesulfonic acid (Aldrich). The resulting salt is removed by gravity filtration of the neat material.
Ethoxylated(10) Allyl Alcohol, Intermediate Material B. The preparation used to prepare Intermediate Material A is repeated except that it is conducted in a stirred autoclave and the total ethylene oxide condensed is increased to give the desired H(OCH2CH2)nOCH2CHxe2x95x90CH2 with average n of about 10.
Ethoxylated (24) Allyl Alcohol, Intermediate Material B1. The preparation used to prepare Intermediate Material A is repeated except that the total ethylene oxide condensed is increased to give the desired H(OCH2CH2)nOCH2CHxe2x95x90CH2 with average n of about 24.
Alkoxylated Allyl Alcohol, Intermediate Material C. The preparation used to prepare Intermediate Material A is repeated in the autoclave except that propylene oxide is first condensed with the allyl alcohol and when an average of about 3 units have been condensed, ethylene oxide is condensed until a total average of about 3 propylene oxides and about 7 ethylene oxides have been condensed per allyl alcohol to give the desired final mixed alkoxylate, H(OCH2CH2)n(OCH(CH3)CH2)mOCH2CHxe2x95x90CH2 with average n of about 7 and average m of about 3.
Ethoxylated Allyl Amines
Allyldiethanolamine, Intermediate Material D. Allyl amine (about 228 g, about 4.0 mol, Aldrich) is placed in a 2 liter, stirred autoclave and is heated to about 100xc2x0 C. under about 200 psi pressure of nitrogen gas. Ethylene oxide (about 352 g, about 8.0 mol, Balchem Corp., State Hill, N.Y.) is gradually pumped into the system with care to keep the temperature in the 90-110xc2x0 C. range. After the pressure stabilizes, the autoclave is cooled to room temperature and depressurized. Then, about 435 g of the resulting hydroxyethylated amine (allyldiethanolamine) is removed from the autoclave.
Ethoxylated Allyl Amine, Intermediate Material E. The approximate 145 g (about 1 mol) of allyldiethanolamine D remaining in the autoclave is treated with about 21.6 g (about 0.1 mol) of 25% sodium methoxide in methanol (Aldrich) and the methanol is removed from the system by stirring and applying vacuum and gradually raising the temperature to about 100xc2x0 C. After the methanol is removed, ethylene oxide is added gradually, keeping the temperature in the 100-110xc2x0 C. range. Addition is continued until a total of about 8 moles of ethylene oxide has been added during the base catalyzed phase of the ethoxylation. After the pressure stabilizes, the system is cooled to about 50xc2x0 C. and about 248 g (about 0.5 mol) of ethoxylated allylamine is withdrawn and the strong base is neutralized by adding about 0.05 moles of methanesulfonic acid to give the desired product, CH2xe2x95x90CHCH2N[(CH2CH2O)nH]2 with average n of about 5.
Ethoxylated Allyl Amine, Intermediate Material F. About 0.5 moles of the ethoxylated product E remaining in the autoclave is again raised to about 100xc2x0 C. and about 220 g (about 5 mol.) ethylene oxide is condensed under the same conditions used previously. After the pressure stabilizes, the autoclave is cooled and about 234 g of the product is removed and neutralized as before to give the desired product, CH2xe2x95x90CHCH2N[(CH2CH2O)nH]2 with average n of about 10.
Ethoxylated Allyl Amine, Intermediate Material F1. About 0.25 moles of the ethoxylated product remaining in the autoclave is again raised to about 100xc2x0 C. and about 264 g (about 6 mol.) ethylene oxide is condensed under the same conditions used previously. After the pressure stabilizes, the autoclave is cooled and the product is removed and neutralized as before to give the desired product, CH2xe2x95x90CHCH2N[(CH2CH2O)nH]2 with average n of about 22.
Etherification of Ethoxylated Allyl Amine
Methyl Capped Ethoxylated Allyl Amine, Intermediate Material G. Ethoxylation of allylamine is conducted as described in the above example to prepare a sample of about 497 g (about 1 mol.) CH2xe2x95x90CHCH2N[(CH2CH2O)nH]2 with average n=5 (Intermediate Material E). However, in this case, the ethoxylated reaction product is not removed from the autoclave, but is further treated with about 216 g (about 1.0 mol) of 25% sodium methoxide in methanol and then the methanol is completely stripped from the autoclave by applying vacuum and raising the temperature gradually to about 100xc2x0 C. with good stirring. After all the methanol is removed, the reaction mixture is cooled to room temperature and about 500 ml of tetrahydrofuran is added, followed by gradually adding about 50.5 g (about 1.0 mol.) chloromethane (Aldrich). The reaction mixture is stirred vigorously and after the initial exotherm, the temperature is raised and held at about 60xc2x0 C. for one hour. Then an additional about 1.0 moles of sodium methoxide is added and the methanol and tetrahydrofuran are removed under vacuum as before. Tetrahydrofuran is again added as a solvent and another about 50.5 g (about 1.0 mol.) of chloromethane is added as before and allowed to react. After the chloromethane has reacted, the reaction mixture is removed from the autoclave and salts are removed by filtration. The tetrahydrofuran is removed by stripping under vacuum to yield an oil from which a small amount of additional salt is removed by filtration to give the desired methyl capped, ethoxylated allylamine, CH2xe2x95x90CHCH2N[(CH2CH2O)nCH3]2 with average n of about 5.
Methyl Capped Ethoxylated Allyl Amine, Intermediate Materials G1 and G2. The process is repeated with the more highly ethoxylated samples F and F1 of allylamine prepared earlier to give the desired capped materials, CH2xe2x95x90CHCH2N[(CH2CH2O)nCH3]2, with average n of about 10 and 22, respectively.
Hydroxyisobutyl Capped Ethoxylated Allylamine, Intermediate Material H. Ethoxylation of allylamine is repeated as described above, but after the ethoxylation has reached a degree of about 10, the CH2xe2x95x90CHCH2N[(CH2CH2O)nH]2 (n=about 10, Intermediate Material F) in the autoclave still containing strong alkaline catalyst, is further treated with two moles of isobutene oxide (BASF) for each mole of ethoxylated intermediate. Heating is continued at about 100-110xc2x0 C. until all the isobutene oxide is consumed and the reaction mixture is then cooled and removed from the reactor and the strong base catalyst is neutralized by adding methanesulfonic acid. This produces the desired ethoxylated allylamine with hindered alcohol termini, CH2xe2x95x90CHCH2N[(CH2CH2O)nxe2x80x94CH2C(OH)(CH3)2]2 with average n of about 10.
Ethoxylated Allylamine with Hindered Alcohol Capping Group Derived from a Glycidyl Ether, Intermediate H1.
Ethoxylation of allylamine is repeated as described above, but after the ethoxylation has reached a degree of about 10, the CH2xe2x95x90CHCH2N[(CH2CH2O)nH]2 (n=about 10, Intermediate Material F) in the autoclave still containing strong alkaline catalyst, is further treated with two moles of glycidyl methyl ether for each mole of ethoxylated intermediate. Heating is continued at about 100-110xc2x0 C. until all the glycidyl methyl ether is consumed and the reaction mixture is then cooled and removed from the reactor and the strong base catalyst is neutralized by adding methanesulfonic acid. This produces the desired ethoxylated allylamine with hindered alcohol termini, CH2xe2x95x90CHCH2N[(CH2CH2O)nxe2x80x94CH2C(OH)CH2OCH3]2 with average n of about 10.
Ether Capping of Alkoxylated Allyl Alcohol
Methyl Capped Ethoxylated Allyl Alcohol, Intermediate Material J. A portion of about 27.8 g (about 0.1 mole) of allyl alcohol with degree of ethoxylation equal to about 5 (Intermediate Material A) is dissolved in about 200 ml of tetrahydrofuran in a 500 ml round bottom flask equipped with magnetic stirring, condenser and set up for blanketing with argon. Sodium hydride (about 2.7 g, about 0.11 mol.) is added in portions to the stirred reaction mixture and after the initial exotherm, mild heating to about 50xc2x0 C. is continued until gas evolution stops. The reaction mixture is cooled to about 10xc2x0 C. and the condenser is replaced by a solid CO2 condenser. Then, gaseous methyl bromide is passed into the reaction mixture until an excess is present and the reaction mixture is stirred and the temperature is allowed to rise to near room temperature. After about 4 hours, the reaction mixture is filtered and then the solvent is removed under vacuum on a rotary evaporator to leave the desired methyl ether of ethoxylated allyl alcohol, CH3(OCH2CH2)nOCH2CHxe2x95x90CH2 with average n of about 5.
Methyl Capped Ethoxylated Allyl Alcohol, Intermediate Material J1 and J2. The same procedure is repeated with the more highly ethoxylated allyl alcohols prepared as described (Intermediates B and B1) to give additional samples of CH3(OCH2CH2)nOCH2CHxe2x95x90CH2 with average n of about 10 and 24, respectively.
Methyl Capped Alkoxylated Allyl Alcohol, Intermediate J3. The same procedure is applied to Intermediate Material C to obtain the corresponding methyl ether of the mixed propoxylated-ethoxylated allyl alcohol.
Hindered Alcohol-Capped Ethoxylated Allyl Alcohol, Intermediate J4. Allyl alcohol is ethoxylated in an autoclave as previously described to an ethoxylation degree of about 20. Prior to neutralizing the basic catalyst, the ethoxylated material is further treated with 1 mole of isobutene oxide (BASF) for each mole of ethoxylated intermediate. Heating is continued at about 100-110xc2x0 C. until all the isobutene oxide is consumed and the reaction mixture is then cooled and removed from the reactor and the strong base catalyst is neutralized by adding methanesulfonic acid. This produces the desired ethoxylated(20) allyl alcohol capped with a xe2x80x94CH2C(CH3)2(OH) group.
Tetrahydropyranyl Ether of Ethoxylated Allyl Alcohol
Tetrahydropyranyl Ether of Ethoxylated Allyl Alcohol, Intermediate Material K. A portion of about 27.8 g (about 0.1 mole) of allyl alcohol with degree of ethoxylation equal to about 5 (Intermediate Material A) is dissolved in about 50 ml of methylene chloride in a 250 ml round bottom flask equipped with magnetic stirring, condenser and set up for blanketing with argon. Then, 3,4-dihydro-2H-pyran (about 16.8 g, about 0.2 mol, Aldrich) is added along with about 0.1 g p-toluenesulfonic acid monohydrate (Aldrich) and the system is allowed to stir at room temperature for about 6 hours. The acid catalyst is neutralized by adding a small excess of base in the form of about 0.15 g of 25% sodium methoxide in methanol (Aldrich) and the solvent and excess dihydropyran are stripped off on the rotary evaporator and salts are removed by filtration to yield the desired tetrahydropyranyl ether, THPxe2x80x94(OCH2CH2)nOCH2CHxe2x95x90CH2 with average n of about 5.
Intermediate Material K1 and K2. The preparation of Intermediate Material K is repeated except that ethoxylated allyl alcohols with degree of ethoxylation of about 10 and 24 (Intermediate Materials B and B1) are used to give the desired tetrahydropyranyl ethers of ethoxylated (10) allyl alcohol and ethoxylated (24) allyl alcohol, Intermediate Materials K1 and K2.
Allyl Ether of Imidazole Ethoxylate
Intermediate Material M. Allyl alcohol is ethoxylated using basic catalysis to a degree of about 10. A portion of about 49.8 g (about 0.10 mol) of the resulting allyl ethoxylate is placed in a 250 ml round bottom flask equipped with reflux condenser, dropping funnel, magnetic stirring and argon blanketing, and about 1 g of N,N-dimethylformamide (Aldrich) is added. Then the reaction mixture is heated to about 70xc2x0 C. with vigorous stirring as about 14.3 g (about 0.12 mol) thionyl chloride is added dropwise over about one hour. Heating is continued for about 18 hours and the excess thionyl chloride is removed by stripping on a rotary evaporator. The resulting oil is then added with vigorous stirring to a 500 ml round bottom flask containing about 80 g (about 1.0 mol) of imidazole and the reaction mixture is heated to about 80xc2x0 C. and held there for about 18 hours. The reaction mixture is cooled and about 21.6 g (about 0.1 mole) of about 25% sodium methoxide in methanol is added and then the methanol and excess imidazole are stripped off on the rotary evaporator and the kugelrohr to give an oil with a salt precipitate. The salt is removed by filtration to yield the imidazole-terminated allyl ethoxylate, CH2xe2x95x90CHCH2(OCH2CH2)n-imidazole where average n is about 10. 
Hydrosilation of Ethers of Ethoxylated Allyl Alcohol with Alkoxysilanes
Intermediate Hydrosilation Material N. A portion of about 29.2 g (about 0.1 mol.) of CH3(OCH2CH2)nOCH2CHxe2x95x90CH2 with average n of about 5 (Intermediate Material J) is placed in a 250 ml round bottom flask equipped with magnetic stirring, distillation head, dropping funnel, and argon blanketing and about 125 ml of toluene is added. The solution is brought to a boil and about 25 ml of toluene is distilled out along with traces of moisture. The distillation head is replaced with a reflux condenser, about 0.1 g (about 0.00024 mol.) chloroplatinic acid (Aldrich) is added, and the solution is brought to reflux. Then about 20 g triethoxysilane (about 0.12 mol, Aldrich) is added dropwise over about 30 minutes and the reflux is continued for about 4 hours. The reaction mixture is cooled and the solvent and excess silane are stripped on a rotary evaporator to give the desired hydrosilated product, CH3(OCH2CH2)nOCH2CH2CH2Si(OCH2CH3)3 with n of about 5.
Intermediate Hydrosilation Material N1. The procedure for preparing Intermediate Material N is repeated except methyldiethoxysilane is substituted for the triethoxysilane. This yields the desired diethoxysilane, CH3(OCH2CH2)nOCH2CH2CH2Si(CH3)(OCH2CH3)2 with average n of about 5.
Hydrosilation of Ethers of Ethoxylated Allyl Alcohol with Cyclic Hydrosiloxanes
Intermediate Hydrosilation Material O. A portion of about 51 g (about 0.1 mol.) portion of CH3(OCH2CH2)nOCH2CHxe2x95x90CH2 with n of about 10, prepared as above (Intermediate Material J1) is placed in a 250 ml. Round bottom flask equipped with magnetic stirrer, argon blanketing, and a distillation head. A portion of about 100 ml. of toluene is added and about 25 ml. of toluene are distilled off to dry the system. The distillation head is replaced by a reflux condenser. A portion of about 6 g (about 0.025 mol.) of 1,3,5,7-tetramethylcyclotetrasiloxane (Gelest Inc., Tullytown, Pa., is added along with about a 20 xcexcL portion of platinum-divinyltetramethyldisiloxane complex in xylene (Gelest), and the reaction mixture is heated to reflux for about 5 hours. After reflux, an aliquot shows an NMR spectrum that indicates substantially all the allyl groups have reacted. The solvent is stripped off to yield the desired ethoxylate-substituted cyclotetrasiloxane, [Si(O)(CH3)CH2CH2CH2(OCH2CH2)10OCH3]4.
Intermediate Hydrosilation Material P. The synthesis of Intermediate Material O is repeated except that the methyl capped ether is replaced by the tetrahydropyranyl-capped ether, THPxe2x80x94(OCH2CH2)nOCH2CHxe2x95x90CH2 (Intermediate Material K1) with average n of about 10, prepared as above. A portion of about 0.5 g of triethylamine is also added to ensure that the system remains slightly alkaline. This yields the desired THP-capped ethoxylate-substituted cyclotetrasiloxane, [Si(O)(CH3)CH2CH2CH2(OCH2CH2)10Oxe2x80x94THP]4.
Intermediate Hydrosilation Material P1. The synthesis is repeated, except that more highly ethoxylated THP ether (Intermediate Materials K2), is used to obtained the desired cyclotetrasiloxane [Si(O)(CH3)CH2CH2CH2(OCH2CH2)24Oxe2x80x94THP]4.
Hydrosilation of Ethers of Ethoxylated Allylamine with Cyclic Hydrosiloxanes
Intermediate Hydrosilation Material Q. A portion of about 52.5 g (about 0.1 mol.) of CH2xe2x95x90CHCH2N[(CH2CH2O)nCH3]2 with average n of about 5, prepared as above (Intermediate Material G) is placed in a 250 ml. Round bottom flask equipped with magnetic stirrer, argon blanketing, and a distillation head. A portion of about 100 ml. of toluene is added and about 25 ml. of toluene is distilled off to dry the system. The distillation head is replaced by a reflux condenser. A portion of about 6 g (about 0.025 mol.) of 1,3,5,7-tetramethylcyclotetrasiloxane (Gelest) is added along with a 20 xcexcL portion of platinum-divinyltetramethyldisiloxane complex in xylene (Gelest), and the reaction mixture is heated to reflux for about 8 hours, after which an aliquot shows an NMR spectrum that indicates substantially all the allyl groups have reacted. The solvent is stripped off to yield the desired aminoethoxylate-substituted cyclotetrasiloxane, [Si(O)(CH3)CH2CH2CH2N{(OCH2CH2)5OCH3}2]4.
N-Allylethylenediamine
Intermediate Material R. A portion of about 120 g (about 2.0 mol.) of ethylenediamine is dissolved in about 300 ml of tetrahydrofuran in a 1000 ml round bottom flask equipped with magnetic stirring, reflux condenser and argon blanketing. A portion of about 76 g (about 1.0 mol.) of allyl chloride is added dropwise with good stirring over about one hour and then the system is brought to reflux for about 30 minutes. The reaction mixture is stripped to near dryness and about 300 ml of water and about 41 g (about 1.02 equivalents) sodium hydroxide is added with care to make the system strongly basic. The resulting solution is cooled to room temperature and extracted twice with about 200 ml portions of diethyl ether. The ether extracts are combined and dried over sodium sulfate and then fractionally distilled to yield a major fraction consisting of N-allylethylenediamine intermediate material suitable for use in hydrosilation reactions.
Hydrosilation of Allylethylenediamine by Cyclic Hydrosiloxanes
Intermediate Hydrosilation Material S. A portion of about 24 g (about 0.1 mol.) of 1,3,5,7-tetramethylcyclotetrasiloxane (Gelest) is dissolved in about 100 ml of dry toluene in a 250 ml, round bottom flask equipped with magnetic stirrer, reflux condenser and argon blanketing. A portion of about 40 g (about 0.40 mol.) of allylethylenediamine made as described above (Intermediate Material R) is added along with a portion of about 0.2 g (about 0.0005 mol.) of chloroplatinic acid (Aldrich), and the system is heated to reflux for about 4 hours. At this point, an aliquot examined by proton NMR shows that the resonances associated with the allyl group are substantially gone. The solvent is stripped off to yield the desired amino-functional cyclotetrasiloxane, [Si(O)(CH3)(CH2CH2CH2NHCH2CH2NH2)]4.
Vinyl-Terminated Oligosiloxanes with Pendant Amino Functionality
Intermediate Material T. In a 1000 ml, round bottom flask equipped with magnetic stirring, dropping funnel, thermometer, and a short fractionation column topped by a distillation head, is placed about 260.5 g (about 2.0 mol) vinyldimethylethoxysilane (Gelest) and about 191.3 g (about 1.0 mol) 3-aminopropylmethyldiethoxysilane. The reaction is stirred at room temperature as about 36 g (about 2 mol) water is added dropwise. The temperature is gradually increased until ethanol is being distilled from the reaction mixture and held at about 120xc2x0 C. until no further ethanol is evolved. This gives the desired intermediate 
where the average value of n is about 1.
Preparation of Vinyl-Terminated Oligosiloxanes with Pendant Ethoxylate Functionality
Intermediate Material U. In a 1000 ml, round bottom flask equipped with magnetic stirring, dropping funnel, thermometer, and a short fractionation column topped by a distillation head, is placed about 260.5 g (about 2.0 mol) vinyldimethylethoxysilane (Gelest) and about 426 g (about 1 mol) of the ethoxylate-substituted triethoxysilane prepared as above, CH3(OCH2CH2)nOCH2CH2CH2Si(OCH2CH3)3 with n of about 5. (Intermediate Material N). The reaction mixture is stirred at room temperature as about 36 g (about 2 mol) water is added dropwise. The temperature is gradually increased until ethanol is being distilled from the reaction mixture and is then held at about 120xc2x0 C. until no further ethanol is evolved. This gives the desired intermediate 
where the average value of n is about 1.
Polysiloxane Intermediates with Pendant Imidazole Groups
Intermediate Material V. Following generally the method of Fortuniak and Chojnowski, Polym. Bull. (Berlin) (1997), 38(4), 371-378, N-allylimidazole hydrochloride is hydrosilated methyldichlorosilane to a high yield of N-[3-(methyldichlorosilyl)propyl]imidazole hydrochloride which is hydrolyzed under controlled conditions to give a mixture of cyclic and linear polysiloxanes with pendant imidazole groups having the general structure 
This mixture is used as intermediate V for incorporation of pendant imidazole groups into other polysiloxanes by re-equilibration.
Imidazole-Terminated Polydimethylsiloxane
Intermediate Material W. In a 250 ml, round bottom flask equipped with magnetic stirrer, reflux condenser, and argon blanketing are placed about 45 g (about 0.1 mol, Gelest) hydride-terminated polydimethylsiloxane with molecular weight of about 450 and about 17.5 g (about 0.23 mol, Aldrich) allyl chloride and about 0.6 g (about 0.0015 mol, Aldrich) chloroplatinic acid. The reaction mixture is heated to about 90xc2x0 C. with stirring for about 18 hours. Excess allyl chloride is stripped out on a kugelrohr apparatus to give the chloropropyl terminated oligomer. Then, imidazole (about 68 g, about 1 mol, Aldrich) and 50 ml of dioxane are added and the reaction mixture is heated under reflux for 16 hours. Then, the reaction mixture is cooled to room temperature and sodium methoxide (about 10.8 g, about 0.20 moles as a 25% solution in methanol) is added. After stirring and allowing to stand for about 3 hours, the system is filtered and the filtrate is stripped of solvent and excess imidazole on a rotary evaporator and then on a kugelrohr at 150xc2x0 C. for 2 hours at a vaccum of about 1 mmHg. to give the desired imidazole-terminated silicone with average n equal to about 5. 